JP2001510177A - Process for producing 6,10- and 6,9-dimethyl-5,10-undecadienyl-2-one - Google Patents
Process for producing 6,10- and 6,9-dimethyl-5,10-undecadienyl-2-oneInfo
- Publication number
- JP2001510177A JP2001510177A JP2000503044A JP2000503044A JP2001510177A JP 2001510177 A JP2001510177 A JP 2001510177A JP 2000503044 A JP2000503044 A JP 2000503044A JP 2000503044 A JP2000503044 A JP 2000503044A JP 2001510177 A JP2001510177 A JP 2001510177A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- alkyl
- transition metal
- undecadienyl
- dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 30
- 230000008569 process Effects 0.000 title claims description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 7
- -1 alkyl acetoacetate Chemical compound 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 150000001449 anionic compounds Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 150000002891 organic anions Chemical class 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 229910052723 transition metal Inorganic materials 0.000 claims 3
- 150000003624 transition metals Chemical class 0.000 claims 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- 229910052785 arsenic Inorganic materials 0.000 claims 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 2
- 239000003638 chemical reducing agent Substances 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- 239000011591 potassium Substances 0.000 claims 2
- 229910052700 potassium Inorganic materials 0.000 claims 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims 1
- 150000008052 alkyl sulfonates Chemical class 0.000 claims 1
- 239000000010 aprotic solvent Substances 0.000 claims 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims 1
- 125000005228 aryl sulfonate group Chemical group 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 150000002941 palladium compounds Chemical class 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- 239000012279 sodium borohydride Substances 0.000 claims 1
- 229910000033 sodium borohydride Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 230000007306 turnover Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- ZDZHCIAFSISUHF-UHFFFAOYSA-N 6,10-dimethylundeca-5,10-dien-2-one Chemical compound CC(=C)CCCC(C)=CCCC(C)=O ZDZHCIAFSISUHF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】 本発明は、触媒系として遷移金属化合物およびリン成分の存在下、場合によってはプロトン性添加剤の存在下に、アルキルアセトアセテートを用いてイソプレンをテロメル化することによって、６，１０−および６，９−ジメチル−５，１０−ウンデカジエニル−２−オンを製造する方法に関する。引続き、このようにして得られたβ−ケトエステルはけん化され、前記の化合物へと脱カルボキシル化される。 (57) [Summary] The present invention provides for the telomerization of isoprene with alkyl acetoacetate in the presence of a transition metal compound and a phosphorus component as a catalyst system, and optionally in the presence of a protic additive, to provide 6,10- and 6,6- The present invention relates to a method for producing 9-dimethyl-5,10-undecadienyl-2-one. Subsequently, the β-ketoester thus obtained is saponified and decarboxylated to the abovementioned compounds.
Description
【０００１】 本発明は、触媒として遷移金属化合物使用下に、アルキルアセトアセテートを
用いてイソプレンをテロメル化し、引続き、得られたβ−ケトエステルをけん化
し、および脱カルボキシル化することによって、６，１０−および６，９−ジメ
チル−５，１０−ウンデカジエニル−２−オンを製造する方法に関する。The present invention provides for the telomerization of isoprene with alkyl acetoacetate using a transition metal compound as a catalyst, followed by saponification and decarboxylation of the resulting β-ketoester to give 6,10 -And 6,9-dimethyl-5,10-undecadienyl-2-one.
【０００２】 非対称ジエン、イソプレンを使用する場合、１位または３位、ならびに二重結
合内位のＥ，Ｚ−異性にある求核剤の攻撃方向のイソプレン単位結合型を考慮し
ながら、１２の可能なテロマー生成物が生じる。When an asymmetric diene, isoprene, is used, taking into account the isoprene unit bond type in the attack direction of the nucleophile at the 1- or 3-position and the E, Z-isomer of the double bond, A possible telomer product results.
【０００３】 この数は、複数の酸水素原子を有する求核剤を使用する際に増大される。[0003] This number is increased when using nucleophiles with multiple oxyhydrogen atoms.
【０００４】 １２の可能なテロマー生成物のうち３つが、必要とされる、天然と同様の頭−
尾結合型を有する。従来、公知技術水準からは、生成物中でこの型のテロマーが
とにかくごくわずかに検出されうるような方法だけが公知である。[0004] Three of the twelve possible telomer products have the required, natural-like head-
It has a tail-joined type. Heretofore, only the methods known from the prior art are such that only very little telomers of this type can be detected in the product.
【０００５】 オクタジエニル−炭化水素鎖の製造法は、J.Berger, J. fur prakt. Chem. 32
7 (1985) 634 から公知である。[0005] The process for producing octadienyl-hydrocarbon chains is described in J. Berger, J. fur prakt. Chem. 32
7 (1985) 634.
【０００６】 前記明細書に記載された方法で、頭−尾結合に関しては、８％未満の選択性が
得られる。[0006] The method described in the above specification gives a selectivity of less than 8% for head-to-tail bonds.
【０００７】 G.Hata, J. Org. Chem. 1971 (15), 2116 およびZakharkin 他, Zh. Org. Khi
m 1988, (24), 2325 の場合、前記の反応の際、望まれる頭−尾結合を有する化 合物の発生に関しては指摘されていない。しかし、前記の型の化合物、殊にα−
ゲラニルアセトンは、ビタミン−Ｅ合成の際の基本成分として重要である。[0007] G. Hata, J. Org. Chem. 1971 (15), 2116 and Zakharkin et al., Zh. Org. Khi.
In the case of m 1988, (24), 2325, no mention is made of the generation of compounds having the desired head-to-tail bond during the above reaction. However, compounds of the above type, especially α-
Geranyl acetone is important as a basic component in vitamin-E synthesis.
【０００８】 本発明の課題は、生成物として、価値のある中間化合物であることが判明した
前記の化合物、ひいては誘導体が得られる方法を提供することである。It is an object of the present invention to provide a process by which the above-mentioned compounds, which have been found to be valuable intermediate compounds, and thus derivatives, are obtained as products.
【０００９】 本発明の対象は、遷移金属化合物とリン成分とからなる触媒系の存在下に、ア
ルキルアセトアセテートを用いてイソプレンをテロメル化することによって、６
，１０−および６，９−ジメチル−５，１０−ウンデカジエニル−２−オンを製
造する方法であり、この方法は、場合によっては一般式： Ｒ1−ＯＨ （Ｉ）、またはThe object of the present invention is to telomerize isoprene with alkyl acetoacetate in the presence of a catalyst system comprising a transition metal compound and a phosphorus component,
, 10- and 6,9-dimethyl-5,10-undecadienyl-2-one, which may optionally comprise the general formula: R 1 —OH (I), or
【００１０】[0010]
【化３】 Embedded image
【００１１】 ［式中、 Ｒ1、Ｒ2、Ｒ3はＣ1〜Ｃ9−Ｃ原子を有する、分枝鎖状または非分枝鎖状のアル キル、Ｃ6〜Ｃ8−Ｃ原子を有するシクロアルキル、アリール、殊にフェニル、ア
リールアルキルを表わし、 Ｘ(-)は無機アニオンまたは有機アニオン、殊にハロゲン化物または硫酸塩を表 わし、 ｙは１または２である］で示されるプロトン性添加剤の存在下に実施され、かつ
こうして得られたβ−ケトエステルが自体公知の方法でけん化され、および脱カ
ルボキシル化されることによって、特徴付けられる。殊に６，１０−異性体は、
本発明の対象である。[Wherein, R 1 , R 2 and R 3 are a branched or unbranched alkyl having a C 1 -C 9 -C atom, and a C 6 -C 8 -C atom. X (-) represents an inorganic or organic anion, particularly a halide or a sulfate, and y is 1 or 2]. It is carried out in the presence of additives and is characterized in that the β-ketoester thus obtained is saponified and decarboxylated in a manner known per se. In particular, the 6,10-isomer is
It is the subject of the present invention.
【００１２】 有機溶剤は、場合によっては使用され、かつ化学反応の範囲内で不活性の挙動
を示すという一般原則を除いて、一定の化合物に限定されない。このことは、例
えば一般式（Ｉ）のアルコールを前記の反応の際に有するような、プロトン化作
用を意味するものではない。Organic solvents are not limited to certain compounds except for the general principle that they are used in some cases and exhibit an inert behavior within the scope of a chemical reaction. This does not imply, for example, a protonation action, such as having an alcohol of the general formula (I) during the reaction.
【００１３】 溶剤は同様に、混合物の形で使用され、この場合、式（Ｉ）による化合物は、
プロトン性添加剤としておよび、溶剤として同時に作用する。The solvent is likewise used in the form of a mixture, in which case the compound according to formula (I)
Acts simultaneously as a protic additive and as a solvent.
【００１４】 芳香族溶剤、例えばベンゾール、トルオールまたはフェノール、ならびにアル
キル基によって置換されたフェノール、ケトンおよび脂肪族アルコールは適当で
ある。Aromatic solvents such as benzol, toluene or phenol, and phenols, ketones and aliphatic alcohols substituted by alkyl groups are suitable.
【００１５】 共触媒として有利に使用されるのは、少なくとも１つの置換基がアルコキシ基
、殊にＣ3基を有するアルコキシ基を表わすような式（ＩＶ）によるリン化合物 である。Preference is given to using phosphorus compounds according to formula (IV) in which at least one substituent represents an alkoxy group, in particular an alkoxy group having a C 3 group, as co-catalyst.
【００１６】 溶剤としてのイソプロパノールとの組合せ物で、特に高い選択性が示される。Particularly high selectivity is shown in combination with isopropanol as solvent.
【００１７】 触媒としては、この場合、好ましくはＰｄ−アセテートが使用される。In this case, Pd-acetate is preferably used as catalyst.
【００１８】 選択的に製造されるα−ゲラニルアセトン（１−頭−尾）とともに生じる３−
頭−尾−異性体は、さらにこの反応の価値のある生成物である。[0018] 3- produced with selectively produced α-geranylacetone (1-head-tail)
The head-tail-isomer is also a valuable product of this reaction.
【００１９】 場合によっては、例えば触媒または生成物を簡単に分離できるように、方法を
数段階で実施することは、有利であることが判明している。In some cases, it has proven to be advantageous to carry out the process in several stages, for example so that the catalyst or the product can be easily separated.
【００２０】 選択性は、温度、溶剤および共触媒を適当に組み合わせることによって制御さ
れることができる。[0020] Selectivity can be controlled by the appropriate combination of temperature, solvent and cocatalyst.
【００２１】 特許の保護を請求されている方法のさらに有利な実施態様は、従属請求項中に
見いだされる。Further advantageous embodiments of the method for which patent protection is sought are found in the dependent claims.
【００２２】 実施例 例１ 保護ガス技術（Ａｒ）の使用下に、酢酸パラジウム１１.２ｍｇ（０.０５ミリ
モル）およびトリフェニルホスファン３９.３ｍｇ（０.１５ミリモル）を、０℃
で、イソプロパノール２０ｍｌと一緒に、電磁拌核コアを備えた５０ｍｌのガラ
スオートクレーブ中に移した。アセト酢酸エチルエステル６ｇおよびイソプレン
６.５ｇの添加後に得られる、均質な黄色の液体を、８０℃で３時間攪拌し、引 続き、氷浴中で室温に冷却した。引続き、過剰のイソプレンを水流真空中で室温
で除去した。EXAMPLES Example 1 Using protective gas technology (Ar), 11.2 mg (0.05 mmol) of palladium acetate and 39.3 mg (0.15 mmol) of triphenylphosphane were added at 0 ° C.
And together with 20 ml of isopropanol into a 50 ml glass autoclave equipped with a magnetically stirred core. The homogeneous yellow liquid obtained after addition of 6 g of ethyl acetoacetate and 6.5 g of isoprene was stirred at 80 ° C. for 3 hours and subsequently cooled to room temperature in an ice bath. Subsequently, the excess isoprene was removed at room temperature in a water-jet vacuum.
【００２３】 反応混合物中に含有されるエチル−２−（ジメチルオクタジエニル）−β−ケ
トエステルを、さらに後処理することなくけん化し、かつ脱カルボキシル化した
。その上、反応混合物を、水酸化ナトリウム３.８ｇ、水１５ｍｌおよびメタノ ール３０ｍｌの添加後、室温で１６時間攪拌した。８０℃の回転型蒸発器で、溶
剤の大部分を除去した後、混合物に水３０ｍおよび濃硫酸６.４ｇを添加し、か つ二酸化炭素がそれ以上生じなくなるまで（約１時間）、還流下に加熱した。ト
ルオール各５ｍｌを用いて３回抽出後、硫酸ナトリウムと一緒に合わせた抽出液
を乾燥した。粗製生成物のガスクロマトグラフィー分析により、６，１０−ジメ
チルー５，１０−ウンデカジエン−２−オンへの選択率３０％（テロマー画分に
対して）の場合、２９％（使用されるイソプレンに対して）のイソゲラニルアセ
トンの収率が判明した。The ethyl-2- (dimethyloctadienyl) -β-ketoester contained in the reaction mixture was saponified and decarboxylated without further work-up. In addition, the reaction mixture was stirred for 16 hours at room temperature after addition of 3.8 g of sodium hydroxide, 15 ml of water and 30 ml of methanol. After removing most of the solvent on a rotary evaporator at 80 ° C., 30 m of water and 6.4 g of concentrated sulfuric acid are added to the mixture and the mixture is refluxed until no more carbon dioxide is produced (about 1 hour). Heated. After three extractions using 5 ml of toluene each, the extract combined with sodium sulfate was dried. Gas chromatographic analysis of the crude product shows that with a selectivity to 6,10-dimethyl-5,10-undecadien-2-one of 30% (based on the telomer fraction), 29% (based on the isoprene used). The yield of isogeranylacetone was determined.
【００２４】 例２〜４０： 例１の場合と同様に行なった。この場合に使用したイソプロパノール２０ｍｌ
の添加剤を、第１表の他の化合物それぞれ２０ｍｌと交換した。これに関して示
されているのは、代謝回転数(Turn Over Number)（モル生成物モルPd -1）、ＴＯ
Ｎ、ならびにテロマー画分に対する６，１０−ジメチル−５，１０−ウンデカジ
エン−２−オンへの選択率、１−ＫＳである。Examples 2 to 40: Performed as in Example 1. 20 ml of isopropanol used in this case
Was replaced with 20 ml each of the other compounds in Table 1. Shown in this context are the Turn Over Number (mol product mol Pd -1 ), TO
N, as well as selectivity to 6,10-dimethyl-5,10-undecadien-2-one for the telomer fraction, 1-KS.
【００２５】 第１表：使用される添加剤および反応温度に依存した代謝回転数（モル生成物モ
ルPd -1）および頭−尾−選択率（テロマー分画に対する）、（ｎPd：ｎP：ｎアセト 酢酸エステル ：ｎイソフ゜レン＝１：３：９２０：１９２０，ｔ＝３ｈ）。Table 1: Turnover numbers (mol product mol Pd -1 ) and head-to-tail selectivity (relative to telomer fraction), depending on the additives used and the reaction temperature, (n Pd : n P : N acetoacetate ester : n isopropylene = 1: 3: 920: 1920, t = 3h).
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】 例４１〜６９ 例１の場合と同様に行なった。イソプロパノール２０ｍｌの代わりに、表に記
載の化合物２０ｍｌを使用した。トリフェニルホスファンを、表に記載の他のリ
ン化合物と交換した。これに関して示されているのは、代謝回転数(Turn Over N
umber)（モル生成物モルPd -1）、ＴＯＮ、ならびにテロマー画分に対する、６，
１０−ジメチル−５，１０−ウンデカジエン−２−オンへの選択率、１−ＫＳで
ある。Examples 41-69 The procedure was as in Example 1. Instead of 20 ml of isopropanol, 20 ml of the compounds listed in the table were used. Triphenylphosphane was exchanged for other phosphorus compounds listed in the table. Shown in this context is the Turn Over N
umber) (molar product mole Pd -1 ), TON, and telomer fraction, 6,
Selectivity to 10-dimethyl-5,10-undecadien-2-one, 1-KS.
【００２９】 第２表：使用されるリン化合物および添加剤に依存した代謝回転数（モル生成物 モルPd -1）および頭−尾−選択率（テロマー画分に対する）（ｎPd：ｎP：ｎアセト 酢酸エステル ：ｎイソフ゜レン＝１：３：９２０：１９２０，ｔ＝３ｈ）。Table 2: Turnover numbers (mol product mol Pd -1 ) and head-to-tail selectivity (relative to telomer fraction) depending on the phosphorus compounds and additives used (n Pd : n P : n- acetoacetic ester : n- isoprene = 1: 3: 920: 1920, t = 3h).
【００３０】[0030]
【表３】 [Table 3]
【００３１】[0031]
【表４】 [Table 4]
【００３２】[0032]
【表５】 [Table 5]
【００３３】[0033]
【表６】 [Table 6]
【００３４】[0034]
【表７】 [Table 7]
【００３５】[0035]
【表８】 [Table 8]
【００３６】[0036]
【表９】 [Table 9]
【手続補正書】特許協力条約第３４条補正の翻訳文提出書[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty
【提出日】平成１２年１月１７日（２０００．１．１７）[Submission date] January 17, 2000 (2000.1.17)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Correction target item name] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【化１】 ［式中、 Ｒ1、Ｒ2、Ｒ3はＣ1〜Ｃ9−Ｃ原子を有する、分子鎖状または非分子鎖状のアル キル、Ｃ6〜Ｃ8−Ｃ原子を有するシクロアルキル、アリール、殊にフェニル、ア
リールアルキルを表わし、 Ｘ(-)は無機アニオンまたは有機アニオンを表わし、 ｙは１または２である］で示されるプロトン性添加剤の存在下に実施し、こうし
て得られたβ−ケトエステルを自体公知の方法でけん化し、脱カルボキシル化す
ることを特徴とする、６，１０−および６，９−ジメチル−５，１０−ウンデカ
ジエニル−２−オンの製造法。Embedded image [Wherein, R 1 , R 2 , and R 3 represent a C 1 -C 9 -C atom, a molecular chain or a non-molecular chain alkyl, a C 6 -C 8 -C atom-containing cycloalkyl, aryl X (-) represents an inorganic anion or an organic anion, y is 1 or 2], and the thus obtained β -A process for producing 6,10- and 6,9-dimethyl-5,10-undecadienyl-2-one, characterized in that the ketoester is saponified and decarboxylated in a manner known per se.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 69/738 Ｃ０７Ｃ 69/738 Ｚ (72)発明者 ライナー ハーン ドイツ連邦共和国 カールシュタイン ヴ ュルツブルガー シュトラーセ 11 (72)発明者 クラウス フートマッハー ドイツ連邦共和国 ゲルンハウゼン レル ヒェンヴェーク 18 Ｆターム(参考） 4H006 AA02 AC44 AC92 BA25 BA45 BA48 BA53 BB11 BB12 BB14 BB16 BB17 BB21 BB41 BC10 BC31 BC32 BE10 BE23 4H039 CA62 CA66 CL20 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification FI theme coat テ ー マ (Reference) C07C 69/738 C07C 69/738 Z (72) Inventor Liner Hahn Carlstein Würzburger Strasse 11 (72 Inventor Klaus Huttmacher Germany Federal Republic of Germany Gernhausen Ler Henweg 18 F-term (reference) 4H006 AA02 AC44 AC92 BA25 BA45 BA48 BA53 BB11 BB12 BB14 BB16 BB17 BB21 BB41 BC10 BC31 BC32 BE10 BE23 4H039 CA62 CA66 CL20
Claims (14)
の存在下に、アルキルアセトアセテートを用いてイソプレンをテロメル化するこ
とによって、６，１０−および６，９−ジメチル−５，１０−ウンデカジエニル
−２−オンを製造するための方法において、この方法を場合によっては一般式： Ｒ1−ＯＨ （Ｉ）、または 【化１】 ［式中、 Ｒ1、Ｒ2、Ｒ3はＣ1〜Ｃ9−Ｃ原子を有する、分枝鎖状または非分枝鎖状のアル キル、Ｃ6〜Ｃ8−Ｃ原子を有するシクロアルキル、アリール、殊にフェニル、ア
リールアルキルを表わし、 Ｘ(-)は無機アニオンまたは有機アニオンを表わし、 ｙは１または２である］で示されるプロトン性添加剤の存在下に実施し、こうし
て得られたβ−ケトエステルを自体公知の方法でけん化し、脱カルボキシル化す
ることを特徴とする、６，１０−および６，９−ジメチル−５，１０−ウンデカ
ジエニル−２−オンの製造法。1. The method according to claim 1, wherein said isoprene is telomerized with alkyl acetoacetate in the presence of a transition metal compound and a phosphorus or arsenic component as a catalyst system. In the process for preparing -undecadienyl-2-one, the process may optionally comprise the general formula: R 1 -OH (I), or [Wherein R 1 , R 2 and R 3 are a branched or unbranched alkyl having a C 1 -C 9 -C atom, a cycloalkyl having a C 6 -C 8 -C atom. , Aryl, especially phenyl, arylalkyl; X (-) represents an inorganic or organic anion; y is 1 or 2] in the presence of a protic additive of the formula A method for producing 6,10- and 6,9-dimethyl-5,10-undecadienyl-2-one, wherein the β-ketoester is saponified and decarboxylated by a method known per se.
添加剤に代えて、Ｃ−原子１〜６個を有する脂肪族カルボン酸、アリールスルホ
ン酸またはアルキルスルホン酸を使用する、請求項１記載の方法。2. In addition or in place of the protic additive according to formula (I) or (II), use is made of an aliphatic carboxylic acid, arylsulfonic acid or alkylsulfonic acid having 1 to 6 C atoms. The method of claim 1, wherein
れるアルキルアセトアセテート１当量とを反応させる、請求項１または２記載の
方法。3. At least 2 equivalents of isoprene and the general formula: [Wherein, R a branched or unbranched C 1 -C 4 - alkyl] reacting an alkyl acetoacetate 1 equivalent represented by the method of claim 1 or 2.
遷移金属もしくはその化合物からなる触媒系、および一般式： Ａ（Ｒ4Ｒ5Ｒ6） （ＩＶ） ［式中、同一であるかまたは異なって、 Ｒ4Ｒ5Ｒ6は分枝鎖状または非分枝鎖状の、Ｃ原子１〜８個を有するアルキルま たはアルコキシ、Ｃ原子６〜８個を有するシクロアルキル、アリール、殊に場合
によっては置換された、有利に第２位および／または第５位でアルキルによって
置換されたフェニル、アリールアルキル、水素を表わし、 Ａはリン、砒素を表わす］で示される化合物からなる共触媒の存在下に反応を実
施する、請求項１から３までのいずれか１項記載の方法。4. A catalyst system comprising a transition metal of Groups 9 and 10 of the Periodic Table (IUPAC 1985) or a compound thereof, and a general formula: A (R 4 R 5 R 6 ) (IV) R 4 R 5 R 6 may be the same or different and may be a branched or unbranched alkyl or alkoxy having 1 to 8 C atoms, a cycloalkyl having 6 to 8 C atoms. Alkyl, aryl, especially phenyl, arylalkyl, optionally substituted, preferably substituted by alkyl in the 2nd and / or 5th position, hydrogen, A represents phosphorus, arsenic] 4. The process according to claim 1, wherein the reaction is carried out in the presence of a cocatalyst consisting of a compound.
、−ＮＲ1Ｒ2Ｈ(+)または−ＣＯＯＨ、 ［式中、Ｒ1およびＲ2は前記の意味を表わす］の１つの基によって、それ自体置
換されている、請求項４記載の方法。5. The method according to claim 1, wherein at least one of the substituents R 4 R 5 R 6 is a group: OH, —NR 1 H
, -NR 1 R 2 H (+) or -COOH, [wherein, R 1 and R 2 are as defined above] by a single group, are themselves substituted, The method of claim 4.
塩、カルボン酸塩、炭酸塩、ホウ酸塩、クエン酸塩、臭化物、塩化物、ヨウ化物
、水酸化物、硝酸塩、硫酸塩、アリールスルホネートまたはアルキルスルホネー
ト、アセチルアセトネート、パラジウムビスベンゾニトリルまたはカリウムテト
ラパラデートを使用する、請求項１から５までのいずれか１項記載の方法。6. A transition metal compound, especially a palladium compound, acetate, carboxylate, carbonate, borate, citrate, bromide, chloride, iodide, hydroxide, nitrate, sulfate 6. The process according to claim 1, wherein an arylsulfonate or alkylsulfonate, acetylacetonate, palladium bisbenzonitrile or potassium tetraparadate is used.
応を実施する、請求項１から６までのいずれか１項記載の方法。7. The process according to claim 1, wherein the reaction is carried out in the presence of a compound which acts as a reducing agent for the transition metal.
、亜鉛粉末またはマグネシウムを使用する、請求項７記載の方法。8. The method according to claim 7, wherein sodium borohydride, potassium borohydride, zinc powder or magnesium is used as the reducing agent.
１〜１０当量を使用する、請求項１から８までのいずれか１項記載の方法。9. The process as claimed in claim 1, wherein 1 to 10 equivalents of the compound of the formula IV are used per equivalent of the transition metal or its ions.
素状金属１ｌの変換に十分である、請求項１から９までのいずれか１項記載の方
法。10. The process according to claim 1, wherein the amount of transition metal compound used is sufficient for the conversion of 10 -4 to 1 g of atoms / l of elemental metal.
求項１から１０までのいずれか１項記載の方法。11. The process as claimed in claim 1, wherein the process is operated at a temperature of from 0 to 130 ° C., in particular from 60 to 100 ° C.
ずれか１項記載の方法。12. The process according to claim 1, wherein the process is carried out in an organic solvent.
トン性溶剤との混合物で使用する、請求項１２記載の方法。13. The process according to claim 12, wherein the compound of formula (I) is used as a solvent, optionally in a mixture with an aprotic solvent.
カジエニル−２−オンおよび６，９−ジメチル−５，１０−ウンデカジエニル−
２−オンを分離する、請求項１から１１までのいずれか１項記載の方法。14. A reaction mixture comprising 6,10-dimethyl-5,10-undecadienyl-2-one and 6,9-dimethyl-5,10-undecadienyl-
The method according to any one of claims 1 to 11, wherein the 2-one is separated.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19730546A DE19730546A1 (en) | 1997-07-17 | 1997-07-17 | Process for the preparation of 6,10- and 6,9-dimethyl-5,10-undecadienyl-2-ones |
| DE19730546.6 | 1997-07-17 | ||
| PCT/EP1998/003647 WO1999003811A1 (en) | 1997-07-17 | 1998-06-17 | Method for producing 6,10 and 6,9-dimethyl-5,10-undecadienyl-2-ones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001510177A true JP2001510177A (en) | 2001-07-31 |
Family
ID=7835929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000503044A Pending JP2001510177A (en) | 1997-07-17 | 1998-06-17 | Process for producing 6,10- and 6,9-dimethyl-5,10-undecadienyl-2-one |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US6310259B1 (en) |
| EP (1) | EP0996609A1 (en) |
| JP (1) | JP2001510177A (en) |
| CN (1) | CN1264357A (en) |
| DE (1) | DE19730546A1 (en) |
| WO (1) | WO1999003811A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8558030B2 (en) * | 2008-08-12 | 2013-10-15 | Dow Global Technologies Llc | Process for telomerization of butadiene |
| ES2755761T3 (en) | 2010-12-21 | 2020-04-23 | Dow Global Technologies Llc | Process for telomerization of butadiene using a mono-orthoalkoxy substituted catalyst |
| US20170275235A1 (en) * | 2016-03-23 | 2017-09-28 | International Flavors & Fragrances Inc. | Method for selective palladium-catalyzed telomerization of substituted dienes |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1289043B (en) * | 1967-02-01 | 1969-02-13 | Basf Ag | Process for the preparation of 6, 10, 14-trimethylpentadecatriene- (5, 9, 14) -one- (2) |
| US3998872A (en) * | 1970-10-05 | 1976-12-21 | Universal Oil Products Company | Preparation of unsaturated carbonyl compounds |
| JPS5411291B2 (en) * | 1972-10-05 | 1979-05-14 | ||
| DE3163383D1 (en) * | 1980-07-10 | 1984-06-07 | Rhone Poulenc Sante | Process for the selective addition of a compound having an activated carbon atom to a substituted conjugated diene |
| FR2657871B1 (en) * | 1990-02-08 | 1993-02-05 | Rhone Poulenc Sante | PROCESS FOR THE PREPARATION OF TERPENIC KETONES. |
-
1997
- 1997-07-17 DE DE19730546A patent/DE19730546A1/en not_active Withdrawn
-
1998
- 1998-06-17 CN CN98807200.9A patent/CN1264357A/en active Pending
- 1998-06-17 JP JP2000503044A patent/JP2001510177A/en active Pending
- 1998-06-17 EP EP98936355A patent/EP0996609A1/en not_active Withdrawn
- 1998-06-17 US US09/446,734 patent/US6310259B1/en not_active Expired - Fee Related
- 1998-06-17 WO PCT/EP1998/003647 patent/WO1999003811A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US6310259B1 (en) | 2001-10-30 |
| WO1999003811A1 (en) | 1999-01-28 |
| EP0996609A1 (en) | 2000-05-03 |
| DE19730546A1 (en) | 1999-01-21 |
| CN1264357A (en) | 2000-08-23 |
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